Mixed monosubstituted cyclopentadienyl Ti(IV) derivatives [(eta(5)-C(5)H(4)R)(eta(5)-C(5)H(4)SiMe(3))Ti(SPh)(2)] (R = PPh(2), Ph(2)P=O, Ph(2)P=S) react with carbonylmetal fragments of group 6 to generate heterodinuclear compounds [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)(2)M(CO)(3)], [(eta(5)-C(5)H(4)SiMe(3))(SPh)Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)M(CO)(4)], [(eta(5)-C(5)H(4)P(E)Ph(2))(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-SPh)(2)M(CO)(4)] (M = Mo, W; E = O, S) and [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-E-C(5)H(4)P(E)Ph(2))(&mgr;-SPh)(2)M(CO)(3)] (M = Mo, W; E = S or M = Mo, E = O). All complexes have been characterized by spectroscopic data. The crystal structure of [(eta(5)-C(5)H(4)SiMe(3))Ti(&mgr;-eta(5):kappa-P-C(5)H(4)PPh(2))(&mgr;-SPh)(2)W(CO)(3)] has been determined by X-ray diffraction techniques, and it was confirmed that the titanium precursor acts as a tridentate metalloligand. The complex crystallizes in the orthorhombic system in space group Pna2(1); a = 23.081(2) Å, b = 14.3046(9) Å, c = 11.6892(8) Å; Z = 4.
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